JP5564168B2 - Water-based undercoating composition - Google Patents

Description

  More particularly, the present invention relates to an undercoat paint composition for waterproofing coating films.

  In order to give waterproofing performance to concrete structures such as rooftops, corridors, verandas, and outdoor parking lots of buildings, the main component is tolylene diisocyanate-terminated prepolymer, which is combined with aromatic amines, plasticizers, fillers, etc. A two-component room temperature curable urethane coating waterproofing material is widely used in which the cured agent is mixed and applied at the construction site. When waterproofing is applied to these concrete and mortar bases, primer treatment should be applied to the base material in advance in order to improve the adhesion between the base and the waterproof layer and to prevent the waterproof layer from swelling. Is required.

  There are solvent-based and water-based primers. The solvent-based system is diluted by adding a solvent such as xylene, toluene, or ethyl acetate to the isocyanate-terminated prepolymer obtained by the reaction of polyoxypropylene polyether polyol and tolylene diisocyanate. A one-component solvent-type urethane primer composed of the above solution, or a two-component solvent-type epoxy primer composed of a main agent composed of a bisphenol A-type epoxy resin solution and a curing agent composed of a fatty acid polyamine solution. Because of the use, there are environmental problems, odors, safety issues.

  As an aqueous system, as a urethane resin emulsion type aqueous primer, a two-part aqueous urethane primer composed of a main agent composed of an emulsion mainly composed of polyol and a curing agent composed of liquid MDI such as crude MDI, carbodiimide modified product, or Examples thereof include a two-component aqueous epoxy primer composed of a main agent composed of an emulsion of bisphenol A type epoxy resin and a curing agent composed of an emulsion of fatty acid polyamine.

  Carboxyl group-containing acidic monomers are introduced into the polyol component to stabilize against water, but if a large amount of carboxyl groups is contained, the reaction between the hydroxyl groups and the carboxyl groups tends to occur, and there is a problem in storage properties (Patent Document) 1).

Aqueous sealer composition comprising monomers selected from epoxy group-containing monomers, carboxyl group-containing monomers and salts thereof, amide group-containing monomers, hydroxyl groups and halogen atom-containing monomers as essential constituent monomers Products have been proposed, but they contain epoxy groups and carboxyl groups, and because of the high reactivity of epoxy groups and carboxyl groups, crosslinking proceeds in the particles during polymerization and storage, making the particles harder, There is a problem that the film property is lowered and the water resistance tends to be insufficient (Patent Document 2).
Japanese Patent Laid-Open No. 2-105879 JP-A-11-199825

  Provided is a water-based coating composition for undercoating that has good adhesion to an upper coating material, adhesion after water resistance, and adhesion to an old coating film base.

  The undercoating composition of the present invention is excellent in adhesion to a base such as concrete or mortar and adhesion to a waterproof material which is a top coating. Moreover, the adhesiveness with an old coating film is also excellent, and it can also paint directly on an old coating film. Moreover, the coating film obtained from this composition is excellent also in water resistance, and its adhesiveness after a water resistance test is also high. The composition is aqueous and is more environmentally compatible than conventional solvent systems.

That is, the present invention
(I).
(A) An epoxy group-containing unsaturated monomer having an epoxy group in the molecule and having a polymerizable double bond (b) A hydroxyl group-containing monomer having a hydroxyl group in the molecule and having a polymerizable double bond Saturated monomer (c) obtained by copolymerization of a monomer mixture comprising a ketone group containing a ketone group in the molecule and having a polymerizable double bond (d) and other monomers A water-based undercoating composition comprising the resulting aqueous dispersion (A) and a crosslinking agent (B),
(II).
The aqueous dispersion (A) contains 0.1 to 20 parts by weight of component (a), 0.1 to 40 parts by weight of component (b), 0.1 to 20 parts by weight of component (c), and 20 to 20 parts of component (d). An aqueous base coating composition according to (I), which is obtained by copolymerization of 100 parts by weight of a monomer mixture comprising 99.7 parts by weight,
(III).
The aqueous undercoat coating composition according to (I) or (II), wherein the crosslinking agent (B) is a polyisocyanate crosslinking agent,
(IV).
The aqueous undercoating composition according to (III), wherein the polyisocyanate-based crosslinking agent is a water-dispersed polyisocyanate-based crosslinking agent,
(V).
The ratio of the total number of moles of hydroxyl groups contained in the aqueous dispersion (A) to the total number of moles of isocyanate groups contained in the crosslinking agent (B) is 1: 0.5 to 1: 5.0 ( III) or the water-based undercoating composition according to (IV),
(VI).
The aqueous undercoat coating composition according to any one of (I) to (V), wherein the glass transition temperature of the copolymer contained in the aqueous dispersion (A) is -40 ° C to 50 ° C,
(VII).
The aqueous undercoat coating composition according to any one of (I) to (VI), wherein the aqueous dispersion (A) is a copolymer aqueous dispersion obtained by emulsion polymerization using a reactive emulsifier,
(VIII).
An undercoat paint composition for waterproofing coating film comprising the composition according to any one of (I) to (VII),
(IX).
The water-based undercoat paint composition as described in (VIII), wherein the waterproof film is a urethane waterproof film,
About.

  As a result of repeated research to solve the above problems, the present inventors have found that an epoxy group-containing unsaturated monomer containing an epoxy group in the molecule and having a polymerizable double bond, and a hydroxyl group in the molecule. Hydroxyl-containing unsaturated monomer having a polymerizable double bond and a ketone group-containing unsaturated monomer having a ketone group in the molecule and having a polymerizable double bond, and other monomers It is characterized in that it contains an aqueous dispersion (A) obtained by copolymerizing a monomer mixture comprising: and a water-dispersed polyisocyanate crosslinking agent (B).

  The epoxy group, hydroxyl group, and ketone group of the aqueous dispersion (A) containing both an epoxy group, a hydroxyl group, and a ketone group contribute to the improvement of adhesion to the top coating material, and crosslink with the water-dispersed polyisocyanate. Adhesion with the substrate can be improved.

  By adjusting the glass transition temperature (Tg) of the aqueous dispersion (A) to the range of −40 ° C. to 50 ° C., the strength of the coating film is increased, and further, the adhesion is improved, thereby producing an effect. The invention has been completed.

  The present invention is described in further detail below.

  In the present invention, the aqueous dispersion (A) may be polymerized by any method such as suspension polymerization, bulk polymerization, emulsion polymerization and the like, and preferably emulsion polymerization is generally used. Polymerization methods can be used.

  The epoxy group-containing unsaturated monomer (a) is an epoxy group-containing unsaturated monomer that contains an epoxy group in the molecule and has a polymerizable double bond. For example, glycidyl (meth) acrylate, (meta ) Allyl glycidyl ether, glycidyl vinyl ether, 3,4-epoxycyclohexyl (meth) acrylate and the like. One or more selected from these can be used. Of these, glycidyl methacrylate is preferred. The component (a) is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, particularly 100 parts by weight of the total amount of monomers used in the aqueous dispersion (A). Is preferably used in an amount of 0.7 to 12 parts by weight. If it is less than 0.1 part by weight, the effect of improving adhesion is insufficient, which is not preferable. On the other hand, if it exceeds 20 parts by weight, the durability is lowered and the price is expensive, which is not preferable. The expression “(meth) acrylate” in the present specification represents acrylate and / or methacrylate.

  The hydroxyl group-containing unsaturated monomer (b) is a hydroxyl group-containing unsaturated monomer having a hydroxyl group in the molecule and having a polymerizable double bond, such as 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, Aronics 5700, 4 manufactured by Toagosei Co., Ltd. -Hydroxystyrene, manufactured by Nippon Shokubai Chemical Co., Ltd. HE-10, HE-20, HP-1 and HP-20 (all of which are acrylate oligomers having a hydroxyl group at the terminal), N-methylol (meta) Hydroxyalkyl esters of (meth) acrylic acid such as acrylamide, including hydroxyl groups Ε-caprolactone-modified hydroxyalkylvinyl copolymer compounds obtained by reaction of the compound with ε-caprolactone Placcel FA-1, Placcel FA-4, Placcel FM-1, Placcel FM-4 (above Daicel Chemical Industries, Ltd.) ), TONE M-201 (manufactured by UCC), and polycarbonate-containing vinyl compounds (specifically, HEAC-1 (manufactured by Daicel Chemical Industries, Ltd.)) and other monoethylenically unsaturated monomers having a hydroxyl group are copolymerized. Examples include acrylic polyol having two or more hydroxyl groups in one molecule as a monomer, among which 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferable. Choose from these The component (b) is preferably used in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the total amount of monomers, and more preferably 0.5 to 30 parts. Part by weight, particularly 0.7 to 20 parts by weight, is preferred, and if it is less than 0.1 part by weight, crosslinking with isocyanate is insufficient and the degree of crosslinking is reduced, and this is not preferred. This is not preferable because the hydrophilicity of the resin increases and the water resistance decreases.

  The ketone group-containing unsaturated monomer (c) is a ketone group-containing unsaturated monomer having a ketone group in the molecule and having a polymerizable double bond, such as acrolein, diacetone acrylamide, diacetone. Examples include methacrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, diacetone acrylate, diacetone methacrylate, acetonyl acrylate, 2-hydroxypropyl acrylate-acetyl acetate, and the like. Of these, acrolein and diacetone acrylamide are preferable. One or more selected from these can be used. However, the carboxyl group and the ester group are not ketone groups, and unsaturated monomers having only them are not included in the component (c). The component (c) is preferably used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the total amount of monomers, more preferably 0.5 to 15 parts by weight, particularly 0.7 to 12 parts by weight. Is preferred. If it is less than 0.1 part by weight, the effect of improving adhesion is insufficient, which is not preferable. On the other hand, when the amount exceeds 20 parts by weight, the hydrophilicity of the aqueous dispersion becomes high and the water resistance is lowered, which is not preferable.

  (D) As the other monomer having a polymerizable double bond, a known radically polymerizable monomer can be used. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, i-nonyl acrylate, n- Monofunctional acrylates such as decyl acrylate, n-dodecyl acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, polyethylene glycol and their methacrylates, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, etc. Bifunctional acrylates and their methacrylates, pentaerythritol tetraacrylate DOO, polyfunctional acrylate and their methacrylate such as dipentaerythritol hexaacrylate, styrene, vinyl toluene, methyl styrene, aromatic vinyl monomers such as chlorostyrene and the like. One or more selected from these can be used. The component (d) is preferably used in an amount of 20 to 99.7 parts by weight, more preferably 40 to 98.5 parts by weight, particularly 56 to 97.5 parts by weight, based on 100 parts by weight of the total amount of monomers. Is preferred. As an aqueous dispersion (A), (a), (b), (c), (d) component is 100 weight part in total.

  The glass transition temperature of the copolymer contained in the aqueous dispersion is preferably −40 to 50 ° C., and more preferably 0 to 45 ° C. When it becomes lower than −40 ° C., the coating film becomes brittle, and the adhesion after water resistance tends to decrease. When the temperature is higher than 50 ° C., a large amount of film forming aid is required to form particles, which is not preferable because the film forming aid inhibits water resistance and adhesion.

In the present invention, the glass transition temperature is determined by the following equation.
1 / Tg = Σ (Wi / Tgi)
Tg: Glass transition temperature of the aqueous dispersion (absolute temperature display)
Tgi: Glass transition temperature of homopolymer of monomer i component (absolute temperature display)
Wi: weight fraction of i component in water dispersion,
Moreover, the following value was used as the glass transition temperature (Tgi) of the homopolymer of each monomer component.
Methyl methacrylate 105 ° C
2-Ethylhexyl methacrylate -85 ° C
Glycidyl methacrylate 38 ° C
Hydroxyethyl methacrylate 55 ° C
Diacetone acrylamide 77 ° C
As an emulsifier used for emulsion polymerization, which is a preferred polymerization method of the aqueous dispersion (A) of the present invention, a general emulsifier that can be used for emulsion polymerization can be used. Is preferable. Examples of the reactive emulsifier include those having a polymerizable double bond in one molecule. Specific examples thereof include Adeka Soap ER-10, ER-20, ER-30 and ER-40 manufactured by ADEKA Corporation. SR-10, SR-20, SR-1025, NE-10, NE-20, NE-30, NE-40, SE-10N, Nippon Emulsifier Co., Ltd. Antox-MS-60, RMA-1120, RMA -564, RMA-568, RMA-506, Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, RN-2025, HS-10, HS- from Daiichi Kogyo Seiyaku Co., Ltd. 20, HS-1025, BC05, BC10, BC0515, BC1025, Sanyo Kasei Kogyo Co., Ltd., Eleminol JS-2, Eleminol RS-30, Kao Co., Ltd. Latemul S-18 , S-180A, and the like PD-104, PD-420, PD-430. Among these, Aqualon RN-20, RN-2025, BC10, and BC1025 are preferable.

  In the emulsion polymerization, one or more of these may be mixed. Moreover, it is also possible to use a non-reactive emulsifier together if necessary. The non-reactive emulsifier is not particularly limited as long as it is used in ordinary emulsion polymerization, and examples thereof include ionic and nonionic surfactants.

  Examples of anionic surfactants include fatty acid salts such as sodium oleate, sulfate esters of higher alcohols such as sodium lauryl sulfate, alkylallyl sulfonates such as dodecylbenzene sulfonate and isooctylbenzene sulfonate, Formalin condensed naphthalene sulfonate, sodium dioctyl sulfosuccinate and the like. Typical examples of the cationic surfactant include imidazoline laurate, ammonium hydroxide, laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium, chloride, and the like.

  Examples of the nonionic surfactant include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, Typical examples include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and the like.

  These emulsifiers can be used alone or in combination of two or more. The amount of the reactive emulsifier used is preferably 0.1 to 10 parts by weight, and more preferably 0.15 to 8 parts by weight with respect to 100 parts by weight of the total amount of monomers. An emulsion obtained by polymerization in an amount exceeding 10 parts by weight is not preferred because the water resistance of the coating film tends to deteriorate. On the other hand, when the amount is less than 0.1 part by weight, the polymerization stability is poor, and the resulting emulsion tends to be unstable and produce aggregates. For this reason, the amount of emulsifier is preferably set in accordance with the purpose within the above range.

  The aqueous medium used for the emulsion polymerization only needs to contain water as an essential component, and may contain other organic solvents. Other organic solvents include alcohol solvents such as ethanol and isopropanol; glycol solvents such as propylene glycol; ether solvents such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and propylene glycol dimethyl ether, propylene glycol monobutyl ether acetate, An ester solvent such as CS-12 manufactured by Chisso Corporation may be mentioned, but it is preferable not to contain an organic solvent from the viewpoint of stability during polymerization of the emulsion and the environment.

  The polymerization initiator is not particularly limited, and known ones can be used. For example, persulfates such as ammonium persulfate and potassium persulfate, azobisisobutyronitrile, azobisisovaleronitrile, azobis Azo compounds such as amidinopropane hydrochloride, t-butyl hydroperoxide, dibutyl peroxide, benzoyl peroxide, diisopropyl peroxycarbonate, cumyl peroxy octoate, cumyl peroxyneodecanoate, cumene hydroperoxide, etc. The peroxide is exemplified.

  Furthermore, if necessary, reducing agents such as acidic sodium sulfite, Rongalite, Bruggolite FF-6 (manufactured by Bruggamann Chemical US), L-ascorbic acid, saccharides, amines, copper ions, iron ions, cobalt ions, nickel ions, etc. A redox initiator using a transition metal ion or a chelate compound of the transition metal ion and a chelating agent such as disodium ethylenediaminetetraacetic acid sodium salt can also be used.

  The amount of the polymerization initiator used is preferably 0.01 to 10 parts by weight or 0.015 to 8 parts by weight with respect to 100 parts by weight of the monomer. If the amount exceeds 10 parts by weight, the molecular weight is lowered and the water resistance tends to be lowered during the formation of the coating film.

  The emulsion polymerization temperature and time in the present invention may be appropriately adjusted. For example, the polymerization temperature is preferably 30 ° C. to 95 ° C., and the reaction time is practically 2 to 20 hours.

  The solid content concentration of the aqueous dispersion (A) is preferably 10 to 70% by weight, and more preferably 30 to 60% by weight. When the resin solid content concentration exceeds 70% by weight, the viscosity of the system is remarkably increased, so that it becomes difficult to remove heat generated by the polymerization reaction, or it takes a long time to take out from the polymerization vessel. There is a tendency to become necessary. Further, when the resin solid content concentration is less than 10% by weight, there is no problem in terms of polymerization operation, but the amount of resin generated by one polymerization operation is small, which is disadvantageous in terms of economics. This is disadvantageous in terms of coating workability and coating film performance degradation, such as a reduced coating film thickness.

  A known polyisocyanate crosslinking agent can be used as the crosslinking agent (B). Specifically, generally used water-dispersed polyisocyanate crosslinking agents can be used. A water-dispersible polyisocyanate-based crosslinking agent is a polyisocyanate polymer having a hydrophilic group introduced therein, and can be dispersed in water as fine particles when added to water and stirred.

  Examples of the polyisocyanate constituting the water-dispersible polyisocyanate include aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate; Isocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether isocyanate, (m- or p-) phenylene diisocyanate 4,4'-biphenylene diisocyanate, 3,3'-dimethyl -4,4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate) and other aromatic polyisocyanates; hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4'- Methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or-2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1 An alicyclic diisocyanate compound such as 1,3-cyclopentane diisocyanate or 1,2-cyclohexane diisocyanate can be used, and one or more of these can be used. As such a polyisocyanate compound, a polyisocyanate compound having an isocyanurate structure, a urethane structure, a biuret structure, an allophanate structure, a uretdione structure, a trimer structure, or the like can also be used.

  Specific examples include products manufactured by Sumitomo Bayer Urethane Co., Ltd., Bihijoule 3100, VP2319, VPLS2336, Asahi Kasei Chemicals Corporation, Duranate WE50-100, WB40-100, WT30-100, T20-100, Mitsui Chemicals Polyurethanes, Inc. ) Company products, Takerak WD-720, WD-723, WD-725, WD-730, WB-700, WB-820, WB-920, Nippon Polyurethane Co., Ltd. product AQ-130D, and the like.

  The amount of the crosslinking agent (B) used is such that the molar equivalent ratio (NCO: OH) of the isocyanate group in the crosslinking agent (B) to the hydroxyl group in the aqueous dispersion (A) is 0.5: 1 to 5: It is preferably chosen to give a ratio of 1, preferably 0.7: 1 to 2: 1.

  The undercoating composition of the present invention is used for purposes other than overcoating, and when applied directly to a substrate, or when applied on another coating film and further provided with a coating film, It is used as a primer for improving the adhesion of the film. It can be used as a primer for waterproofing coatings, undercoats, and intermediate coats. Furthermore, it is useful for an aqueous two-component primer composition for waterproofing coating films.

  The aqueous resin composition of the present invention is a pigment such as titanium oxide, a filler such as calcium carbonate, an antifoaming agent, a water-soluble polymer, a preservative, and pH adjustment, as necessary, in the same manner as a normal emulsion coating composition. An agent, a film-forming aid, a plasticizer, a flame retardant, and the like can be added, and it is effective to add a water-soluble resin in order to increase the permeability to the base. The water-soluble resin is not particularly limited, and is preferably added in an amount that does not lower the water resistance, and is preferably added in an amount of 5% to 25% with respect to the solid content of the aqueous resin composition. In addition, the use of a wetting agent is effective for preventing repelling of the old coating film. As the wetting agent, for example, Surfinol 104, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol SE, Surfinol SEF, Surfinol 504, Olphin EXP4001, Olphin EXP4036, Olphin EXP4051 (Nisshin Chemical Industry Co., Ltd.) ) Manufactured), DISCOAT N-14, Neocor P, Neocor SW-C (Daiichi Kogyo Seiyaku Co., Ltd.), Nopco 1338, Nopco 2272-R-SN, Nopco Wet 50, Nopco Wet SN-20T, SN wet 125, SN wet 366, SN wet 970 (manufactured by San Nopco), Neoperex GS, Neoperex G-15, Perex NB-L, Perex OT-P, Emulgen 106, Emulgen 707 (Kao Corporation) Company, Ltd.) and the like.

  Next, although the water-based undercoat coating composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to this Example.

(Synthesis Example 1) Emulsion-1
In a separable flask equipped with a stirrer, a reflux condenser, and a dropping funnel, 78 parts by weight of pure water, Bruggolite FF-6 (manufactured by Bruggamann Chemical US), 0.4 part by weight, 0.013 part by weight of ferrous sulfate, ethylenediamine Add 0.013 parts by weight of disodium tetraacetate, 0.22 parts by weight of Aqualon HS-10 and 0.22 parts by weight of Aqualon RN-20, and adjust to 60 ° C. in a nitrogen stream while stirring. In a separate container, 46 parts by weight of methyl methacrylate, 19 parts by weight of 2-ethylhexyl methacrylate, 9 parts by weight of glycidyl methacrylate, 17 parts by weight of 2-hydroxyethyl methacrylate, 9 parts by weight of diacetone acrylamide, and 2. Aqualon HS-10 as an emulsifier. 03 parts by weight, Aqualon RN-20 2.03 parts by weight, cumene hydroperoxide 0.8 parts by weight, and pure water 44.2 parts by weight were mixed and stirred to prepare an emulsion. The temperature inside the separable flask was maintained at 60 ° C. for 3 hours, and the above mixture was continuously added from the dropping funnel into the separable flask at a constant rate. After completion of the addition, the temperature was maintained at 60 ° C. for 2 hours to complete the reaction, and 27.7 parts by weight of pure water was added to obtain an emulsion-1 having a solid content of 40% by weight.

(Synthesis Examples 2-7) Emulsion-2-7
Using the raw materials described in Table 1 in a polymerization apparatus similar to that shown in Synthesis Example 1, polymerization was performed in the same manner as in Synthesis Example 1 to obtain emulsions 2 to 7.

Example 1
Using Emulsion-1 obtained in Synthesis Example 1, 90 parts by weight of pure water and 10 parts by weight of texanol are added to 100 parts by weight to adjust the solid content to 20%. 13 parts by weight were added, 2.2 parts by weight of Olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 1. Using this compound 1, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water adhesion using a two-component urethane-based waterproofing waterproofing Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. The initial adhesion, water-resistant adhesion, and warm water adhesion using a urethane waterproof membrane were good. The adhesion to the old paint film was also good.

(Example 2)
Using emulsion-1 obtained in Synthesis Example 1, 90 parts by weight of pure water and 10 parts by weight of texanol are added to 100 parts by weight to adjust the solid content to 20%. 13.8 parts by weight of 720 was added, 2.2 parts by weight of olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 2. Using this compound 2, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, and hot-water adhesion using a two-pack urethane-based waterproofing Sarasane C (Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. The initial adhesion, water-resistant adhesion, and warm water adhesion using a urethane waterproof membrane were good. The adhesion to the old paint film was also good.

(Examples 3 to 5)
The emulsion used, texanol, pure water, cross-linking agent and wetting agent were changed as shown in Table 2 to prepare Formulations 3 to 5, and test pieces 1 and 2 were prepared and evaluated in the same manner as in Example 1. Carried out. The results are shown in Table 2. The initial adhesion, water-resistant adhesion, and warm water adhesion using urethane film waterproofing material Saraseine C (Asahi Glass Polyurethane Building Materials Co., Ltd.) were good. The adhesion to the old paint film was also good.

(Example 6)
Using Emulsion-1 obtained in Synthesis Example 1, 90 parts by weight of pure water and 10 parts by weight of texanol are added to 100 parts by weight to adjust the solid content to 20%. As a crosslinking agent, dilanate WE50- 19.4 parts by weight of 100 was added, 2.2 parts by weight of olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 6. Using this compound 6, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, and hot water adhesion using a two-component urethane-based waterproofing membrane Sarasane C (Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. The initial adhesion, water-resistant adhesion, and warm water adhesion using a urethane waterproof membrane were good. The adhesion to the old paint film was also good.

(Comparative Example 1)
Emulsion-3 obtained in Synthesis Example 3 was used, 100 parts by weight of pure water was added to 100 parts by weight, the solid content was adjusted to 20%, no crosslinking agent was used, and olefin was used as a wetting agent. 2.2 parts by weight of EXP4036 was added, and the mixture was stirred with a homogenizer at 1000 rpm for 3 minutes to obtain Formulation 7. Using this compound 7, test specimens 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water using a two-component urethane-based waterproofing membrane Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) Adhesion and old film adhesion were evaluated. The results are shown in Table 2. Since no cross-linking agent was included, the hot water adhesion and the adhesion to the old coating film were reduced.

(Comparative Example 2)
Using Emulsion-4 obtained in Synthesis Example 4, 90 parts by weight of pure water and 10 parts by weight of texanol are added to 100 parts by weight to adjust the solid content to 20%. 6.9 parts by weight, 2.2 parts by weight of Olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 8. Using this compound 8, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water adhesion using a two-component urethane-based coating film waterproof Sarasane C (Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. Since GMA was not used, the adhesion decreased.

(Comparative Example 3)
Using Emulsion-5 obtained in Synthesis Example 5, 90 parts by weight of pure water and 10 parts by weight of texanol were added to 100 parts by weight to adjust the solid content to 20%. 6.9 parts by weight, 2.2 parts by weight of Olefin EXP4036 was added as a wetting agent, and the mixture was stirred with a homogenizer at 1000 rpm for 3 minutes to obtain Formulation 9. Using this compound 9, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water adhesion using a two-component urethane-based waterproofing waterproofing Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. Since DAAM was not used, the hot water adhesion decreased.

(Comparative Example 4)
Using Emulsion-6 obtained in Synthesis Example 6, 80 parts by weight of pure water and 20 parts by weight of texanol were added to 100 parts by weight to adjust the solid content to 20%. 13 parts by weight were added, 2.2 parts by weight of Olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 10. Using this compound 10, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water adhesion using a two-component urethane-based waterproofing membrane Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. Adhesiveness decreased because of a large amount of film forming aid.

(Comparative Example 5)
Emulsion-7 obtained in Synthesis Example 7 was used, 100 parts by weight of pure water was added to 100 parts by weight, the solid content was adjusted to 20%, and 13 parts by weight of Hihijoule 3100 was added as a crosslinking agent. Then, 2.2 parts by weight of olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 11. Using this compound 11, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water adhesion using a two-component urethane-based waterproofing waterproofing Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. Since the glass transition temperature was low, the hot water adhesion decreased.

(Comparative Example 6)
Using Emulsion-3 obtained in Synthesis Example 3, 100 parts by weight of pure water was added to 100 parts by weight, adjusted to a solid content of 20%, and 4.6 parts by weight of adipic acid dihydrazide as a crosslinking agent. Then, 2.2 parts by weight of olefin EXP4036 was added as a wetting agent, and the mixture was stirred for 3 minutes at 1000 rpm with a homogenizer to obtain Formulation 12. Using this compound 12, test pieces 1 and 2 were prepared, and initial adhesion, water-resistant adhesion, hot water adhesion using a two-component urethane-based waterproofing membrane Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) And adhesion of the old coating film were evaluated. The results are shown in Table 2. The water-resistant adhesion, hot water adhesion, and adhesion to the old coating film also decreased.

(Preparation of test piece 1)
Using the formulation blended in the examples, a flexible plate (150 × 70 × 3 mm) was brush-coated at a coating amount of 100 g / m ² . After drying at room temperature for 24 hours, cloth adhesive tape NO. 102N (Nichiban Co., Ltd. product) is pasted, and two-component urethane-based waterproofing membrane Sarasane C (Asahi Glass Polyurethane Building Materials Co., Ltd.) is applied to a thickness of 1 to 2 mm and cured at room temperature for 7 days. Test piece 1 was obtained.

(Preparation of test piece 2)
A solvent-based one-component urethane primer Sarasenu P (Asahi Glass Polyurethane Building Materials Co., Ltd.) was used, and a flexible plate (150 × 70 × 3 mm) was applied with a coating amount of 100 g / m ² . After drying at room temperature for 24 hours, a two-component urethane-based waterproofing membrane Sarasane C (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) was applied to a thickness of 1 to 2 mm and cured at room temperature for 1 day. Furthermore, 100 g / m ² of a two-component solvent-based urethane coating Sarasane T (manufactured by Asahi Glass Polyurethane Building Materials Co., Ltd.) was brushed, cured at room temperature for 24 hours, and baked at 50 ° C. for 7 days. The formulation blended in this example was used for this substrate, and a coating amount of 100 g / m ² was applied by brush. After curing at room temperature for 24 hours, cloth adhesive tape NO. 102N (Nichiban Co., Ltd. product) is pasted, and two-component urethane film waterproofing material Sarasane C (Asahi Glass Polyurethane Building Materials Co., Ltd.) is applied to a thickness of 1 to 2 mm and cured at room temperature for 7 days. Test piece 2 was obtained.

(Adhesion test)
(A) Initial adhesion Using the test piece 1, a 180 degree peel test was conducted according to JIS K6854-2.
(B) Water-resistant adhesiveness Using test piece 1, without side sealing and back sealing, completely immersed in pure water at room temperature, left for 7 days, taken out from pure water, and wiped off the water on the coating surface. . Evaluation was made in the same manner as in the initial adhesion test, and the water adhesion resistance was evaluated.
(C) Hot water adhesion The test piece 1 was used, and it was completely immersed in 50 degreeC warm water, without performing a side seal and a back seal, and after leaving for 7 days, it took out from warm water and wiped off the water | moisture content of the coating-film surface. Evaluation was made in the same manner as in the initial adhesion test, and the hot water adhesion was evaluated.
(D) Old film initial stage adhesiveness Using the test piece 2, the 180 degree | times peel test was done according to JISK6854-2.
(E) Old paint film hot water adhesion Using test piece 2, without side seal and back seal, completely immersed in 50 ° C warm water, left for 7 days, taken out from the warm water, and wiped the moisture on the paint film surface. It was. Evaluation was made in the same manner as in the previous coating film initial adhesion test, and the old coating film warm water adhesion evaluation was made.
(Peel test evaluation)
Evaluation criteria ○: Waterproofing material cohesive failure. Δ: Partially peeled interface. X: The interface between the primer and the waterproof material is peeled off.

Claims (8)

(A) An epoxy group-containing unsaturated monomer having an epoxy group in the molecule and having a polymerizable double bond (b) A hydroxyl group-containing monomer having a hydroxyl group in the molecule and having a polymerizable double bond Saturated monomer (c) obtained by copolymerization of a monomer mixture comprising a ketone group containing a ketone group in the molecule and having a polymerizable double bond (d) and other monomers obtained water dispersion (a) and a water-soluble primer coating composition you containing polyisocyanate crosslinking agent (B), the aqueous primer coating composition characterized by underlying is old coating.   The aqueous dispersion (A) contains 0.1 to 20 parts by weight of component (a), 0.1 to 40 parts by weight of component (b), 0.1 to 20 parts by weight of component (c), and 20 to 20 parts of component (d). The aqueous undercoat paint composition according to claim 1, which is obtained by copolymerization of 100 parts by weight of a monomer mixture comprising 99.7 parts by weight.   The aqueous undercoating composition according to claim 1 or 2, wherein the polyisocyanate-based crosslinking agent is a water-dispersed polyisocyanate-based crosslinking agent.   The ratio of the total number of moles of hydroxyl groups contained in the aqueous dispersion (A) to the total number of moles of isocyanate groups contained in the crosslinking agent (B) is from 1: 0.5 to 1: 5.0. Item 4. The aqueous undercoat paint composition according to any one of Items 1 to 3.   The water-based undercoating composition according to any one of claims 1 to 4, wherein the copolymer contained in the aqueous dispersion (A) has a glass transition temperature of -40 ° C to 50 ° C.   The aqueous undercoating composition according to any one of claims 1 to 5, wherein the aqueous dispersion (A) is a copolymer aqueous dispersion obtained by emulsion polymerization using a reactive emulsifier. An undercoat paint composition for waterproofing coating film comprising the composition according to any one of claims 1 to 6 . The water-based undercoat paint composition according to claim 7 , wherein the waterproof coating material is a urethane waterproof coating material.